Analysis of several emerging contaminants (steroids, caffeine and methylparaben) in water using automated solid-phase microextraction with comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (SPME-GCxGC–ToF/MS) is presented. Experimental design was used to determine the best SPME extraction conditions and the steroids were not derivatized prior to injection. SPME-GCxGC–ToF/MS provided linear ranges from 0.6 to 1200 μg L−1 and limits of detection and quantitation from 0.02 to 100 μg L−1. A series of river water samples obtained locally were subjected to analysis. SPME-GCxGC–ToF/MS is readily automated, straightforward and competitive with other methods for low level analysis of emerging contaminants